CA2353965A1 - Method for producing a self-supporting metal film - Google Patents
Method for producing a self-supporting metal film Download PDFInfo
- Publication number
- CA2353965A1 CA2353965A1 CA002353965A CA2353965A CA2353965A1 CA 2353965 A1 CA2353965 A1 CA 2353965A1 CA 002353965 A CA002353965 A CA 002353965A CA 2353965 A CA2353965 A CA 2353965A CA 2353965 A1 CA2353965 A1 CA 2353965A1
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- metal
- base layer
- cathode
- roller
- roller cathode
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0315—Oxidising metal
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/04—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching
- H05K3/046—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching by selective transfer or selective detachment of a conductive layer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Electrolytic Production Of Metals (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to a method for producing a self-supporting metal film (40), especially copper film, which has a lower cohesive strength due to its microstructure and which can be formed so as to produce sharp edges. According to the invention, a base layer is deposited on the cylinder cathode (22) in a galvanic manner. A cauliflower-like structure (60) is adherently deposited from the metal onto the metal base layer (58) by means of an additional anode (32) between the cylinder cathode (22) and the anode basket (24). The metal film (40) consisting of the metal base layer (58) and the cauliflower-like structure (60) is removed from the cylinder cathode (22), rinsed and dried.
The dried film (40) consisting of the metal base layer (58) which is provided with the cauliflower-like structure (60) is moved through a black oxide bath (46), whereupon rinsing and drying occurs.
The dried film (40) consisting of the metal base layer (58) which is provided with the cauliflower-like structure (60) is moved through a black oxide bath (46), whereupon rinsing and drying occurs.
Description
Process for producing a self-supporting metal foil The invention concerns a process for producing a self-supporting foil, in particular a copper foil, which by virtue of its constitution has a low shearing strength and can be structured in a sharp-edged configuration, wherein the metal foil is galvanically deposited on a rotating roller which forms a cathode and which is dipped into an electrolyte bath containing ions of the metal, an anode cage is provided at a constant spacing from the roller cathode and a defined adjustable do volitage is applied during rotation of the roller cathode to the roller cathode and the anode cage so that a given adjustable high direct current flows between the roller cathode and the anode cage in the electrolyte bath, by which direct current a metal base layer is deposited on the roller cathode, at least one additional anode is provided between the roller cathode and the anode cage, a defined adjustable second do voltage is applied between the roller cathode and the additional anode so that a given adjustable <~dditional direct current flows between the roller cathode and the additional anode, whereby a cauliflower structure comprising the metal is deposited in firmly adhering relationship on the outside of the metal base layer, whiich is remote from the roller cathode, the metal foil comprising the metal base layer provided with the cauliflower structure is detached from the roller cathode, and the metal foil comprising the metal base layer provided wif:h the cauliflower structure is rinsed and dried.
EP 0 063 347 discloses a metal foil which is used as a stamping foil and which is transferred on to a substrate by means of a suitable stamping member. In order to fix that known metal foill which can be structured in a sharp-edged configuration to the above-mentioned substrate, use is made of an adhesive which is preferably a hot meld adhesive. Such an adhesive represents an electrically insulating layer so that electrically conductive contacting of the metal foil which can be structured in a sharp-edged configuration with the substrate is not possible there. In regard to ~lectrieally insulating substrates, that is not a material consideration, but t s the circumstances are different in regard to ohmically conducting substrates.
EP 0 392 151 A2 proposes integrating solder powder particles into the adhesive layer between the metal foil and the substrate in order to make an electrically conducting connection between a substrate and such a metal fail which can be structured in a sharp-edged configuration.
Irrespective of whether solder powder particles are or are not integrated into the adhesive layer, the metal foil which can be structured in a sharp-edged configuration requires the adhesive layer to be applied to the side of the foil, which is towards the substrate. That represents a not inconsiderable production complication and expenditure.
US-A 5 0i9 221 discloses an apparatus for the galvanic production of a metal foil such as a copper foil, on a roller cathode which dips into an electrolyte bath containing ions of the metal. An anode cage is disposed at i5 a spacing from the roller cathode. The anode cage is in concentric relationship with the roller cathode. A defined do voltage is applied to the roller cathode and the anode cage. The roller cathode is driven in rotation at the same time. As a result of the do voltage a given high direct current flows between the roller cathode and the anode cage, with the metal foil thus being deposited on the roller cathode in the form of a metal base layer. On its outside which is remote from the roller cathode, that known metal foil involves a relatively low degree of surface roughness. The surface roughness of a copper foil produced in that Hray is at a maximum between 5 and 6 ~.m. As a consequence of that degree of surface roughness, it has not been possible hitherto for such a known metal or copper foil to be applied directly to a substrate, while being structured in a sharp-edged configuration, without an adhesive layer.
US Nos 4 692 221 or 5 215 646 each .disclose a process of the kind set forth in the opening part of this specification, for producing a metal foil, in particular a copper foil, which in comparison with a metal foil and in particular a copper foil without a cauliflower structure, as a consequence of its increased surface roughness, enjoys improved adhesion after having been embossed on to a substrate.
c The object of the invention is so to develop a process of the kind set forth in the opening part of this specification that it is possible to produce a metal foil, in particular a copper foil, whose adhesive strength after embossing on to a substrate is still further improved.
In accordance with the invention in a process of the kind set forth in the opening part of this specification, that object is attained in that the dried metal foil comprising the metal base layer provided with the cauliflower structure is moved through a black oxide bath, and the metal foil comprising the metal base layer provided with the cauliflower structure, 1o subsequently to the black oxide bath, is rinsed and dried.
The process steps according to the invention provide that the shearing strength of the metal foil when ennbossed on to a substrate is further improved.
The anode cage can be for example at: a constant spacing from the roller cathode, which for example can be of the order of magnitude of around 50 mm. The at least one additional anode between the anode cage and the roller cathode can for example have an anode bar which is at a constant spacing from the roller cathode, which spacing can be of the order of magnitude of between 2 and 3 mm. The metal base layer, in particular 2o copper, is deposited on the rotating roller caithode by means of the anode cage. Depending on the do voltage applied to the roller cathode and the anode cage, and the direct current flowing therebetween, that base layer can be of the order of magnitude of between 10 and 100 ~.m. The at least one additional anode between the roller cathode and the anode cage, depending on the second do voltage appllied between them and the additional direct current produced thereby, produces the cauliflower structure consisting of the metal or the copper, on the metal, in particular copper. base layer. That cauliflower structure involves a surface roughness of between 10 and 25 ~.m The metal foil, in particular the copper foil, consisting of the base layer and the cauliflower structure therefore advantageously entails such a level of surface roughness that the caulifllower structure is hookingly engaged to the substrate, thus affording a hiigh level of shearing strength for the foil on the substrate virtually independently of the material of the substrate. The substrate may be for example an electrically or ohmically conducting body. If such a body is embossed with the foil produced in accordance with the invention, in a condition of being structured in a sharp-edged configuration, it can be used for example as a resistance heating element. The foil produced in accordance wiith the invention can also be applied to an electrically insulating substrate in a' condition of being structured in a sharp-edged configuration, in order for example to produce a circuitry structure with a high power consumption. It is likewise possible for the foil which is produced in accordance with the invention and which can be structured in a sharp-edged configuration to be embossed on to a substrate having an adhesive layer, or for the foil to be provided with an adhesive layer in order for it to be embossed on to any substrate in a condition of being structured in a sharp-edgecl configuration.
i5 It is desirable if the speed of rotation oi= the roller cathode and the do voltage as between the roller cathode and the anode cage are adapted to each other in order to produce the metal and in particular copper base layer in a given thickness. That means that the thickness of the metal and in particular copper base layer is directly proportional to the do voltage between the roller cathode and the anode cage and consequently to the direct current between the roller cathode and the anode cage and it is inversely proportional to the speed of rotation of the roller cathode.
In order to provide a given thickness or height of the metal cauliflower structure on the metal base layer, the additional do voltage between the additional anode and the roller cathode and the speed of rotation of the roller cathode can be suitably adapted to each other. The consideration in regard to the thickness or height of the metal cauliflower structure on the metal base layer is similar to the thickness of the metal base layer, in that the thickness or height of t:he metal cauliflower structure is directly proportional to the additional do voltage between the additional anode and the roller cathode and the additional direct current flowing therebetween and it is inversely proportional to the speed of rotation.
Consequently, by suitably adjusting the additional do voltage and the speed of rotation of the roller cathode, it is specifically and targetedly possible to adjust the thickness or height of the metal cauliflower structure as desired at between i0 and 25 ~,m. A greater thickness or height for the metal cauliflower structure is less meaningful because then particles of the cauliflower structure become detached therefrom, which is unwanted. A
smaller thickness or height of the metal cauliflower structure than 10 ~,m is also not appropriate because then the adhesive strength of the metal foil produced in accordance with the invention, which can be structured in a sharp-edged configuration, does not enjoy tihe desired shearing strength 1o after being embossed on to a substrate.
In accordance with the invention the metal foil comprising the metal base layer provided with the cauliflower structure is moved after the rinsing and drying operations through a black oxide bath. Subsequently to the black oxide bath, in accordance with the invention a rinsing operation and a drying operation are carried out. The metal foil, in particular a copper foil, which is produced in accordance with the invention in that way and which, by virtue of its constitution, has a low level of shearing strength and consequently can be structured in a sharp-edged configuration by embossing not only has a cauliflower structure by virtue of the treatment in the black oxide bath, but a fibrous hairy cauliflower structure by which the shearing strength of the metal foil embossed to a substrate is advantageously improved.
Further details, features and advantages will be apparent from the description hereinafter of an apparatus which is diagrammatically illustrated in the Figure for carrying out the process according to the invention, a portion on a greatly enlarged scale from a copper foil produced in accordance with the invention and a graph for illustrating the shearing strength of a metal or copper foil produced in accordance with the invention, embossed on to substrates of various plastic materials. In the drawing:
Figure i diagrammatically shows an apparatus for carrying out the process for the production of a metal and in p<jrticular a copper foil, a Figure 2 shows an REM image of a portion of a metal or copper foil produced in accordance with the invention to show the cauliflower structure, Figure 3 shows a detail from Figure 2 on a further enlarged scale to show the fibrously hairy cauliflower structure due to the black oxide bath, and Figure 4 is a graph to illustrate the shearing strength of a metal or copper foil produced in accordance with the invention which has been embossed on to various plastic materials, in comparison with a known metal or copper foil, which by virtue of its nature is of a low shearing strength and which can be structured in a sharp-edged configuration, which has been fixed on a suitable substrate in known manner by means of an adhesive, in particular a melt adhesive.
Figure 1 shows an electrolyte bath 10 which contains an electrolyte 14 in a tank 12. The electrolyte 14 is circulated by means of a pump 16 and a filter or cleaning and regenerating device 18 arranged downstream of the pump. For that purpose, rinsing tubes 20 are provided in the tank 12 of the electrolyte bath 10.
A roller cathode 22 and an anode cage 24 are dipped into the electrolyte 14 of the electrolyte bath 10. The anode cage 24 is definedly spaced from the roller cathode 22; it is arranged concentrically with respect to the roller cathode 22. The rinsing tubes 20 are disposed in the intermediate spaces between the roller cathode 22 and the anode cage 24.
The roller cathode 22 and the anode cage 24 .are connected together with a first do voltage source 26 by means of which a correspondingly high direct current flows in the electrolyte 14 between t:he roller cathode 27 and the anode cage 24. This direct current is the ion flow of the metal or copper ions provided in the electrolyte 14, towards the roller cathode 22. The said ions are deposited on the cylindrical peripheral surface 28 of the roller cathode 22. The roller cathode 22 is driven at a given speed of rotation.
This is indicated by the arcuate arrow 30. The metal or copper ions which are deposited on the cylindrical peripheral surface 28 form on the cylindrical peripheral surface 28 of the roller cathode 22 a metal or copper base layer.
Also provided between the roller cathode 22 and the anode cage 24 is an additional anode 32 which is in the form of a rod or bar and which is oriented in the axial direction of the roller cathode 22. The additional anode 32 is at a substantially smaller spacing from 'the roller cathode 22 than the anode cage 24. The additional anode 32 and the roller cathode 22 are connected together with a second do voltage source 34. The voltage of the first do voltage source 26 and the voltage of the second do voltage source 34 can be set as desired independently of each other. The second do voltage source 34 produces a corresponding metal or copper ion flow in a direction from the additional anode 32 to the roller cathode 22. That additional direct current produces on the outside of the metal base layer, which is remote from the roller cathode 22, a cauliflower structure comprising the metal or the copper, which is deposited on the metal base layer in a firmly adhering condition if the voltage of the second do voltage source 34 is suitably adjusted. The additional anode 32 can be radially displaceable for the same purpose.
The metal base layer which is deposited on the cylindrical peripheral 2o surface 28 of the roller cathode 22 in that 'way, with the 1~irmly adhering cauliflower structure, is continuously detae;hed from the rotating roller cathode 22, deflected around a first deflection roller 36 and moved through a rinsing device 38. In that rinsing device 38~, electrolyte which adheres to the metal foil 40, in particular copper foil, is rinsed off the metal foil 40 and, after regeneration, fed back to the electrolyte bath 10 again. The metal foil 40 which is cleaned in that way is moved subsequently to that rinsing operation through a drying device 4c! in which the metal foil 40 is dried.
Thereafter, the dried metal or copper foil 40 is deflected around a second deflection roller 44 and transported tlhrough a black oxide bath 46.
Such a black oxide bath 46, that is to say the corresponding bath solution, is available on the market comparatively ine:rcpensively. For example, such a black oxide bath solution can be obtained from Blasberg, Riedel, as can be seen from the prospectus from that company 'Verfahrensanleitung ENBOND MB 500', pages 1 through 7.
The metal foil 40 coated with black oxide, when it comes out of the black oxide bath 46, is deflected around a 'third deflection roller 48 and thereafter conveyed through a second rinsing device 50 in which excess black oxide solution is removed from the met<~I, in particular copper foil 40.
The second rinsing device 50 is followed in the direction of transportation movement or advance movement of the metal foil 40 at a downstream location by a second drying device 52 in whicY~ the metal foil comprising the i0 metal base layer and the cauliflower structure provided with black oxide is dried to afford the finished foil product. That finished foil product can then be wound for example on to a bar 54 of a winding reel 56.
Figure 2 shows an REM image of a surface portion of the metal or copper foil 40 according to the invention, in vuhich the cauliflower structure ~5 60 provided in a firmly adhering condition any the metal base layer 58 can be clearly seen. Figure 3 again shows on an extremely enlarged scale the corresponding cauliflower particles 62 of the cauliflower structure 60 of the metal or copper foil 40 in order to show the fiibers or hairs produced by the black oxide on the surface of the cauliflower particles 62.
20 The cauliflower structure 60 and the fibers or hairs of the black oxide, which are formed on the cauliflower particles 62, afford excellent shearing strength for the metal or copper foil 60 produced in accordance with the invention, on substrates comprising various plastic materials, as is shown in a graph view in Figure 4. Figure 4 shows in the z-direction peeling 25 strengths in accordance with IEC 326 in N/mm, in the y-direction a comparison of the peeling strengths of a I<;nown metal foil of the kind described in the opening part of this specification, which is fixed on a substrate comprising the various plastic materials by means of an organic adhesive, in comparison with a metal or copper foil 40 produced in 30 accordance with the invention, which is simply fixed without adhesive on the corresponding substrates by the effect of heat or by hot stamping. The adhesive fixing is clearly shown in the y-direcition by 'min org.' and by 'max org.'. Fixing of the foil 40 produced in accordance with the invention on the corresponding substrate and without adhesive is shown by 'min anorg.' and by 'max anorg'. The x-axis in Figure 4 denotes various plastic materials for the corresponding substrates. It is clearly apparent from Figure 4 that, in the case of a large number of plastic materials, the shearing strength of hot-embossed metal or copper foils according to the invention is considerably improved.
EP 0 063 347 discloses a metal foil which is used as a stamping foil and which is transferred on to a substrate by means of a suitable stamping member. In order to fix that known metal foill which can be structured in a sharp-edged configuration to the above-mentioned substrate, use is made of an adhesive which is preferably a hot meld adhesive. Such an adhesive represents an electrically insulating layer so that electrically conductive contacting of the metal foil which can be structured in a sharp-edged configuration with the substrate is not possible there. In regard to ~lectrieally insulating substrates, that is not a material consideration, but t s the circumstances are different in regard to ohmically conducting substrates.
EP 0 392 151 A2 proposes integrating solder powder particles into the adhesive layer between the metal foil and the substrate in order to make an electrically conducting connection between a substrate and such a metal fail which can be structured in a sharp-edged configuration.
Irrespective of whether solder powder particles are or are not integrated into the adhesive layer, the metal foil which can be structured in a sharp-edged configuration requires the adhesive layer to be applied to the side of the foil, which is towards the substrate. That represents a not inconsiderable production complication and expenditure.
US-A 5 0i9 221 discloses an apparatus for the galvanic production of a metal foil such as a copper foil, on a roller cathode which dips into an electrolyte bath containing ions of the metal. An anode cage is disposed at i5 a spacing from the roller cathode. The anode cage is in concentric relationship with the roller cathode. A defined do voltage is applied to the roller cathode and the anode cage. The roller cathode is driven in rotation at the same time. As a result of the do voltage a given high direct current flows between the roller cathode and the anode cage, with the metal foil thus being deposited on the roller cathode in the form of a metal base layer. On its outside which is remote from the roller cathode, that known metal foil involves a relatively low degree of surface roughness. The surface roughness of a copper foil produced in that Hray is at a maximum between 5 and 6 ~.m. As a consequence of that degree of surface roughness, it has not been possible hitherto for such a known metal or copper foil to be applied directly to a substrate, while being structured in a sharp-edged configuration, without an adhesive layer.
US Nos 4 692 221 or 5 215 646 each .disclose a process of the kind set forth in the opening part of this specification, for producing a metal foil, in particular a copper foil, which in comparison with a metal foil and in particular a copper foil without a cauliflower structure, as a consequence of its increased surface roughness, enjoys improved adhesion after having been embossed on to a substrate.
c The object of the invention is so to develop a process of the kind set forth in the opening part of this specification that it is possible to produce a metal foil, in particular a copper foil, whose adhesive strength after embossing on to a substrate is still further improved.
In accordance with the invention in a process of the kind set forth in the opening part of this specification, that object is attained in that the dried metal foil comprising the metal base layer provided with the cauliflower structure is moved through a black oxide bath, and the metal foil comprising the metal base layer provided with the cauliflower structure, 1o subsequently to the black oxide bath, is rinsed and dried.
The process steps according to the invention provide that the shearing strength of the metal foil when ennbossed on to a substrate is further improved.
The anode cage can be for example at: a constant spacing from the roller cathode, which for example can be of the order of magnitude of around 50 mm. The at least one additional anode between the anode cage and the roller cathode can for example have an anode bar which is at a constant spacing from the roller cathode, which spacing can be of the order of magnitude of between 2 and 3 mm. The metal base layer, in particular 2o copper, is deposited on the rotating roller caithode by means of the anode cage. Depending on the do voltage applied to the roller cathode and the anode cage, and the direct current flowing therebetween, that base layer can be of the order of magnitude of between 10 and 100 ~.m. The at least one additional anode between the roller cathode and the anode cage, depending on the second do voltage appllied between them and the additional direct current produced thereby, produces the cauliflower structure consisting of the metal or the copper, on the metal, in particular copper. base layer. That cauliflower structure involves a surface roughness of between 10 and 25 ~.m The metal foil, in particular the copper foil, consisting of the base layer and the cauliflower structure therefore advantageously entails such a level of surface roughness that the caulifllower structure is hookingly engaged to the substrate, thus affording a hiigh level of shearing strength for the foil on the substrate virtually independently of the material of the substrate. The substrate may be for example an electrically or ohmically conducting body. If such a body is embossed with the foil produced in accordance with the invention, in a condition of being structured in a sharp-edged configuration, it can be used for example as a resistance heating element. The foil produced in accordance wiith the invention can also be applied to an electrically insulating substrate in a' condition of being structured in a sharp-edged configuration, in order for example to produce a circuitry structure with a high power consumption. It is likewise possible for the foil which is produced in accordance with the invention and which can be structured in a sharp-edged configuration to be embossed on to a substrate having an adhesive layer, or for the foil to be provided with an adhesive layer in order for it to be embossed on to any substrate in a condition of being structured in a sharp-edgecl configuration.
i5 It is desirable if the speed of rotation oi= the roller cathode and the do voltage as between the roller cathode and the anode cage are adapted to each other in order to produce the metal and in particular copper base layer in a given thickness. That means that the thickness of the metal and in particular copper base layer is directly proportional to the do voltage between the roller cathode and the anode cage and consequently to the direct current between the roller cathode and the anode cage and it is inversely proportional to the speed of rotation of the roller cathode.
In order to provide a given thickness or height of the metal cauliflower structure on the metal base layer, the additional do voltage between the additional anode and the roller cathode and the speed of rotation of the roller cathode can be suitably adapted to each other. The consideration in regard to the thickness or height of the metal cauliflower structure on the metal base layer is similar to the thickness of the metal base layer, in that the thickness or height of t:he metal cauliflower structure is directly proportional to the additional do voltage between the additional anode and the roller cathode and the additional direct current flowing therebetween and it is inversely proportional to the speed of rotation.
Consequently, by suitably adjusting the additional do voltage and the speed of rotation of the roller cathode, it is specifically and targetedly possible to adjust the thickness or height of the metal cauliflower structure as desired at between i0 and 25 ~,m. A greater thickness or height for the metal cauliflower structure is less meaningful because then particles of the cauliflower structure become detached therefrom, which is unwanted. A
smaller thickness or height of the metal cauliflower structure than 10 ~,m is also not appropriate because then the adhesive strength of the metal foil produced in accordance with the invention, which can be structured in a sharp-edged configuration, does not enjoy tihe desired shearing strength 1o after being embossed on to a substrate.
In accordance with the invention the metal foil comprising the metal base layer provided with the cauliflower structure is moved after the rinsing and drying operations through a black oxide bath. Subsequently to the black oxide bath, in accordance with the invention a rinsing operation and a drying operation are carried out. The metal foil, in particular a copper foil, which is produced in accordance with the invention in that way and which, by virtue of its constitution, has a low level of shearing strength and consequently can be structured in a sharp-edged configuration by embossing not only has a cauliflower structure by virtue of the treatment in the black oxide bath, but a fibrous hairy cauliflower structure by which the shearing strength of the metal foil embossed to a substrate is advantageously improved.
Further details, features and advantages will be apparent from the description hereinafter of an apparatus which is diagrammatically illustrated in the Figure for carrying out the process according to the invention, a portion on a greatly enlarged scale from a copper foil produced in accordance with the invention and a graph for illustrating the shearing strength of a metal or copper foil produced in accordance with the invention, embossed on to substrates of various plastic materials. In the drawing:
Figure i diagrammatically shows an apparatus for carrying out the process for the production of a metal and in p<jrticular a copper foil, a Figure 2 shows an REM image of a portion of a metal or copper foil produced in accordance with the invention to show the cauliflower structure, Figure 3 shows a detail from Figure 2 on a further enlarged scale to show the fibrously hairy cauliflower structure due to the black oxide bath, and Figure 4 is a graph to illustrate the shearing strength of a metal or copper foil produced in accordance with the invention which has been embossed on to various plastic materials, in comparison with a known metal or copper foil, which by virtue of its nature is of a low shearing strength and which can be structured in a sharp-edged configuration, which has been fixed on a suitable substrate in known manner by means of an adhesive, in particular a melt adhesive.
Figure 1 shows an electrolyte bath 10 which contains an electrolyte 14 in a tank 12. The electrolyte 14 is circulated by means of a pump 16 and a filter or cleaning and regenerating device 18 arranged downstream of the pump. For that purpose, rinsing tubes 20 are provided in the tank 12 of the electrolyte bath 10.
A roller cathode 22 and an anode cage 24 are dipped into the electrolyte 14 of the electrolyte bath 10. The anode cage 24 is definedly spaced from the roller cathode 22; it is arranged concentrically with respect to the roller cathode 22. The rinsing tubes 20 are disposed in the intermediate spaces between the roller cathode 22 and the anode cage 24.
The roller cathode 22 and the anode cage 24 .are connected together with a first do voltage source 26 by means of which a correspondingly high direct current flows in the electrolyte 14 between t:he roller cathode 27 and the anode cage 24. This direct current is the ion flow of the metal or copper ions provided in the electrolyte 14, towards the roller cathode 22. The said ions are deposited on the cylindrical peripheral surface 28 of the roller cathode 22. The roller cathode 22 is driven at a given speed of rotation.
This is indicated by the arcuate arrow 30. The metal or copper ions which are deposited on the cylindrical peripheral surface 28 form on the cylindrical peripheral surface 28 of the roller cathode 22 a metal or copper base layer.
Also provided between the roller cathode 22 and the anode cage 24 is an additional anode 32 which is in the form of a rod or bar and which is oriented in the axial direction of the roller cathode 22. The additional anode 32 is at a substantially smaller spacing from 'the roller cathode 22 than the anode cage 24. The additional anode 32 and the roller cathode 22 are connected together with a second do voltage source 34. The voltage of the first do voltage source 26 and the voltage of the second do voltage source 34 can be set as desired independently of each other. The second do voltage source 34 produces a corresponding metal or copper ion flow in a direction from the additional anode 32 to the roller cathode 22. That additional direct current produces on the outside of the metal base layer, which is remote from the roller cathode 22, a cauliflower structure comprising the metal or the copper, which is deposited on the metal base layer in a firmly adhering condition if the voltage of the second do voltage source 34 is suitably adjusted. The additional anode 32 can be radially displaceable for the same purpose.
The metal base layer which is deposited on the cylindrical peripheral 2o surface 28 of the roller cathode 22 in that 'way, with the 1~irmly adhering cauliflower structure, is continuously detae;hed from the rotating roller cathode 22, deflected around a first deflection roller 36 and moved through a rinsing device 38. In that rinsing device 38~, electrolyte which adheres to the metal foil 40, in particular copper foil, is rinsed off the metal foil 40 and, after regeneration, fed back to the electrolyte bath 10 again. The metal foil 40 which is cleaned in that way is moved subsequently to that rinsing operation through a drying device 4c! in which the metal foil 40 is dried.
Thereafter, the dried metal or copper foil 40 is deflected around a second deflection roller 44 and transported tlhrough a black oxide bath 46.
Such a black oxide bath 46, that is to say the corresponding bath solution, is available on the market comparatively ine:rcpensively. For example, such a black oxide bath solution can be obtained from Blasberg, Riedel, as can be seen from the prospectus from that company 'Verfahrensanleitung ENBOND MB 500', pages 1 through 7.
The metal foil 40 coated with black oxide, when it comes out of the black oxide bath 46, is deflected around a 'third deflection roller 48 and thereafter conveyed through a second rinsing device 50 in which excess black oxide solution is removed from the met<~I, in particular copper foil 40.
The second rinsing device 50 is followed in the direction of transportation movement or advance movement of the metal foil 40 at a downstream location by a second drying device 52 in whicY~ the metal foil comprising the i0 metal base layer and the cauliflower structure provided with black oxide is dried to afford the finished foil product. That finished foil product can then be wound for example on to a bar 54 of a winding reel 56.
Figure 2 shows an REM image of a surface portion of the metal or copper foil 40 according to the invention, in vuhich the cauliflower structure ~5 60 provided in a firmly adhering condition any the metal base layer 58 can be clearly seen. Figure 3 again shows on an extremely enlarged scale the corresponding cauliflower particles 62 of the cauliflower structure 60 of the metal or copper foil 40 in order to show the fiibers or hairs produced by the black oxide on the surface of the cauliflower particles 62.
20 The cauliflower structure 60 and the fibers or hairs of the black oxide, which are formed on the cauliflower particles 62, afford excellent shearing strength for the metal or copper foil 60 produced in accordance with the invention, on substrates comprising various plastic materials, as is shown in a graph view in Figure 4. Figure 4 shows in the z-direction peeling 25 strengths in accordance with IEC 326 in N/mm, in the y-direction a comparison of the peeling strengths of a I<;nown metal foil of the kind described in the opening part of this specification, which is fixed on a substrate comprising the various plastic materials by means of an organic adhesive, in comparison with a metal or copper foil 40 produced in 30 accordance with the invention, which is simply fixed without adhesive on the corresponding substrates by the effect of heat or by hot stamping. The adhesive fixing is clearly shown in the y-direcition by 'min org.' and by 'max org.'. Fixing of the foil 40 produced in accordance with the invention on the corresponding substrate and without adhesive is shown by 'min anorg.' and by 'max anorg'. The x-axis in Figure 4 denotes various plastic materials for the corresponding substrates. It is clearly apparent from Figure 4 that, in the case of a large number of plastic materials, the shearing strength of hot-embossed metal or copper foils according to the invention is considerably improved.
Claims
CLAIM
A process for producing a self-supporting foil (40), in particular a copper foil, which by virtue of its constitution has a low shearing strength and can be structured in a sharp-edged configuration, wherein the metal foil (40) is galvanically deposited on a rotating roller (22) which forms a cathode and which is dipped into an electrolyte bath (10) containing ions of the metal, an anode cage (24) is provided at a constant spacing from the roller cathode (22) and a defined adjustable dc voltage is applied during rotation of the roller cathode (22) to the roller cathode (22) and the anode cage (24) so that a given adjustable high direct current flows between the roller cathode (22) and the anode cage (24) in the electrolyte bath (10), by which direct current a metal base layer (58) is deposited on the roller cathode (22), at least one additional anode (32) is provided between the roller cathode (22) and the anode cage (24), a defined adjustable second dc voltages is applied between the roller cathode (22) and the additional anode (32) so that a given adjustable additional direct current flows between the roller cathode (22) and the additional anode (32), whereby a cauliflower structure (60) comprising the metal is deposited in firmly adhering relationship on the outside of the metal base layer (58), which is remote from the roller cathode (22), the metal foil (40) comprising the metal base layer (58) provided with the cauliflower structure (60) is detached from the roller cathode (22), and the metal foil (40) comprising the metal base layer (58) provided with the cauliflower structure (60) is rinsed and dried, characterised in that the dried metal foil (40) comprising the metal base layer (58) provided with the cauliflower structure (60) is moved through a black oxide bath (46), and the metal foil (40) comprising the metal base layer (58) provided with the cauliflower structure (60), subsequently to the black oxide bath (46), is rinsed and dried.
A process for producing a self-supporting foil (40), in particular a copper foil, which by virtue of its constitution has a low shearing strength and can be structured in a sharp-edged configuration, wherein the metal foil (40) is galvanically deposited on a rotating roller (22) which forms a cathode and which is dipped into an electrolyte bath (10) containing ions of the metal, an anode cage (24) is provided at a constant spacing from the roller cathode (22) and a defined adjustable dc voltage is applied during rotation of the roller cathode (22) to the roller cathode (22) and the anode cage (24) so that a given adjustable high direct current flows between the roller cathode (22) and the anode cage (24) in the electrolyte bath (10), by which direct current a metal base layer (58) is deposited on the roller cathode (22), at least one additional anode (32) is provided between the roller cathode (22) and the anode cage (24), a defined adjustable second dc voltages is applied between the roller cathode (22) and the additional anode (32) so that a given adjustable additional direct current flows between the roller cathode (22) and the additional anode (32), whereby a cauliflower structure (60) comprising the metal is deposited in firmly adhering relationship on the outside of the metal base layer (58), which is remote from the roller cathode (22), the metal foil (40) comprising the metal base layer (58) provided with the cauliflower structure (60) is detached from the roller cathode (22), and the metal foil (40) comprising the metal base layer (58) provided with the cauliflower structure (60) is rinsed and dried, characterised in that the dried metal foil (40) comprising the metal base layer (58) provided with the cauliflower structure (60) is moved through a black oxide bath (46), and the metal foil (40) comprising the metal base layer (58) provided with the cauliflower structure (60), subsequently to the black oxide bath (46), is rinsed and dried.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19857157A DE19857157A1 (en) | 1998-12-11 | 1998-12-11 | Process for the production of a self-supporting metal foil |
| DE19857157.7 | 1998-12-11 | ||
| PCT/DE1999/003906 WO2000036188A2 (en) | 1998-12-11 | 1999-12-01 | Method for producing a self-supporting metal film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2353965A1 true CA2353965A1 (en) | 2000-06-22 |
Family
ID=7890715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002353965A Abandoned CA2353965A1 (en) | 1998-12-11 | 1999-12-01 | Method for producing a self-supporting metal film |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6632341B1 (en) |
| EP (1) | EP1149189A2 (en) |
| JP (1) | JP2002532629A (en) |
| AU (1) | AU2276400A (en) |
| CA (1) | CA2353965A1 (en) |
| DE (1) | DE19857157A1 (en) |
| WO (1) | WO2000036188A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10133250B4 (en) * | 2001-07-09 | 2005-06-30 | Vipem Hackert Gmbh | Method for producing an electrical or electronic cable harness in the form of a flexible laminate |
| EP1424882A1 (en) * | 2002-11-26 | 2004-06-02 | I & T Innovation Technology Entwicklungs- und Holding AG | Flat conductor cable |
| DE102007055275A1 (en) * | 2007-11-20 | 2009-05-28 | Hahn-Schickard-Gesellschaft für angewandte Forschung e.V. | Flexible circuit substrate for electrical circuits and method of making the same |
| DE102018120028A1 (en) * | 2018-08-17 | 2020-02-20 | Bolta-Werke Gmbh | Method for producing a metal foil, metal foil, component, electrolyte solution and device |
| CZ2023241A3 (en) * | 2023-06-21 | 2024-10-16 | České vysoké učenà technické v Praze | An equipment for the electrolytic production of copper foils |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE131044C (en) | ||||
| US3198672A (en) * | 1960-08-18 | 1965-08-03 | Internat Protected Metals Inc | Preparation of cupric oxide surfaces |
| US3674656A (en) | 1969-06-19 | 1972-07-04 | Circuit Foil Corp | Bonding treatment and products produced thereby |
| US3901785A (en) | 1972-05-09 | 1975-08-26 | Antonina Vladimiro Buzhinskaya | Apparatus for producing a metal band |
| DD131044B1 (en) * | 1977-02-21 | 1982-11-24 | Heinz Fink | METHOD FOR THE ELECTROLYTIC PRODUCTION OF AN OXIDIC STAINLESS ON COPPER FOILS |
| JPS5687677A (en) | 1979-12-19 | 1981-07-16 | Nippon Mining Co Ltd | Method of producing copper foil for printed circuit |
| DE3116078A1 (en) * | 1981-04-22 | 1983-01-20 | IVO Irion & Vosseler, Zählerfabrik GmbH & Co, 7730 Villingen-Schwenningen | "EMBOSSING FILM" |
| US4409037A (en) * | 1982-04-05 | 1983-10-11 | Macdermid Incorporated | Adhesion promoter for printed circuits |
| US4490218A (en) * | 1983-11-07 | 1984-12-25 | Olin Corporation | Process and apparatus for producing surface treated metal foil |
| US4692221A (en) * | 1986-12-22 | 1987-09-08 | Olin Corporation | In-situ dendritic treatment of electrodeposited foil |
| US5019221A (en) * | 1989-01-18 | 1991-05-28 | Yates Industries | Electroplating drum cathode with high current-carrying capability |
| DE3908097A1 (en) * | 1989-03-13 | 1990-09-20 | Irion & Vosseler | EMBOSSING FILM FOR APPLYING GUIDED TRACKS TO SOLID OR PLASTIC SUBSTRATES |
| US4969958A (en) * | 1989-03-30 | 1990-11-13 | Rd Chemical Company | Process and composition for forming black oxide layers |
| US5215646A (en) * | 1992-05-06 | 1993-06-01 | Circuit Foil Usa, Inc. | Low profile copper foil and process and apparatus for making bondable metal foils |
-
1998
- 1998-12-11 DE DE19857157A patent/DE19857157A1/en not_active Ceased
-
1999
- 1999-12-01 AU AU22764/00A patent/AU2276400A/en not_active Abandoned
- 1999-12-01 WO PCT/DE1999/003906 patent/WO2000036188A2/en not_active Application Discontinuation
- 1999-12-01 US US09/857,832 patent/US6632341B1/en not_active Expired - Lifetime
- 1999-12-01 JP JP2000588432A patent/JP2002532629A/en active Pending
- 1999-12-01 CA CA002353965A patent/CA2353965A1/en not_active Abandoned
- 1999-12-01 EP EP99966835A patent/EP1149189A2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002532629A (en) | 2002-10-02 |
| WO2000036188A2 (en) | 2000-06-22 |
| AU2276400A (en) | 2000-07-03 |
| DE19857157A1 (en) | 2000-06-15 |
| EP1149189A2 (en) | 2001-10-31 |
| US6632341B1 (en) | 2003-10-14 |
| WO2000036188A3 (en) | 2000-11-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |